Chelation as a process following chemisorption upon emitters for field desorption and field ionization mass spectrometry

Acetylacetone (Hacac) admitted as a gas to an ion source containing CoCl₂ adsorbed on a field ionization/field desorption emitter produces the ion [Co(acac)Cl]⁺. Similar ions arising from interaction of adsorbed salt and a ligand admitted as a gas were found for CoCl₂ and trifluoroacetyl acetone, and for FeCl₂ and acetylacetone. The chelation process represents a new kind of reaction of chemisorbed species in field ionization mass spectrometry.     

Electronic structure of epitaxial graphene layers on SiC: effect of the substrate

A strong substrate-graphite bond is found in the first all-carbon layer by density functional theory calculations and x-ray diffraction for few graphene layers grown epitaxially on SiC. This first layer is devoid of graphene electronic properties and acts as a buffer layer. The graphene nature of the film is recovered by the second carbon layer grown on both the (0001) and (0001[over]) 4H-SiC surfaces. We also present evidence of a charge transfer that depends on the interface geometry. Hence the graphene is doped and a gap opens at the Dirac point after three Bernal stacked carbon layers are formed.     

Proton-induced grain boundary segregation in stainless steel

Abstract

A technique is developed which addresses the problem of irradiation assisted stress corrosion cracking of stainless steels in light water reactors using high energy protons to induce grain boundary segregation. These results represent the first grain boundary segregation measurements in bulk produced by proton irradiation of stainless steel. The technique allows the study of grain boundary composition with negligible sample activation, short irradiation time, rapid sample turnaround and at minimal cost. Scanning Auger electron microscopy is used to obtain grain boundary composition measurements of irradiated and unirradiated samples of ultra high purity (UHP) type 304L stainless steel and UHP type 304L steels with the additions of phosphorus (UHP + P) and sulphur (UHP + S). Results show that irradiation of all three alloys causes significant Ni segregation to the grain boundary and Cr and Fe away from it. Irradiation of the UHP + P alloy also results in segregation of P at the grain boundary from 5.3 to 8.7 at %, over 80 times the bulk value. No radiation-induced grain boundary segregation of S was measured in the UHP + S alloy. Results also indicate that the presence of P or S may enhance radiation-induced segregation of major alloying elements at the boundary. Comparison of irradiated and unirradiated regions of the UHP + P alloy indicate that while a prior thermal treatment segregates P to the grain boundary to 5.3 at %, the major element concentrations at the grain boundary are completely different from those under irradiation.     

Quantum Monte Carlo study of the CO interaction with a dimer model surface for Cr(110)

The chemisorption of CO on a Cr (110) surface is investigated using the quantum Monte Carlo method in the diffusion Monte Carlo (DMC) variant and a model Cr₂CO cluster. The present results are consistent with the earlier ab initio HF study with this model that showed the tilted/near-parallel orientation as energetically favoured over the perpendicular arrangement. The DMC energy difference between the two orientations is larger (1.9 eV) than that computed in the previous study. The distribution and reorganization of electrons during CO adsorption on the model surface are analysed using the topological electron localization function method that yields electron populations, charge transfer and clear insight on the chemical bonding that occurs with CO adsorption and dissociation on the model surface.     

Characterization of aromatic-thiol π-type hydrogen bonding and phenylalanine-cysteine side chain interactions through ab initio calculations and protein database analyses

In this study, the aromatic-thiol π hydrogen bonding and phenylalanine-cysteine side chain interactions are characterized through both molecular orbital calculations on a C₆H₆-HSCH₃ model complex and database analyses of 609 X-ray protein structures. The aromatic-thiol π hydrogen bonding interaction can achieve a stabilization energy of 2.60 kcal mol^?1, and is stronger than the already documented aromatic-hydroxyl and aromatic-amino hydrogen bonds. However, the occurrence of the aromatic-thiol hydrogen bond is rather rare in proteins. This is because most of the thiol groups participate in the formation of either disulphide bonds or stronger S—H…O (or N) ‘normal’ hydrogen bonds in a protein environment. Interactions between the side chains of phenylalanine and cysteine residues are characterized as the phenyl(Phe)(HSCH₂-)(Cys) interaction. The bonding energy for such interactions is approximately 3.71 kcal mol-¹ and is achieved in a geometric arrangement with an optimal phenyl(Phe)-(HS-)(Cys) π-type hydrogen bonding interaction. The interaction is very sensitive to the orientation of the two lone electron pairs on the sulphur atom relative to the π electron cloud of the phenyl ring. Accordingly, the interaction configurations that can accomplish a significant bonding energy exist only within a narrow configurational space. The database analysis of 609 experimental X-ray protein structures demonstrates that only 268 of the 1620 cysteine residues involve such phenylalanine-cysteine side chain interactions. Most of these interactions occur in the form of π (aromatic)-lone pair(sulphur) attractions, and correspond to a bonding energy less than 1.5 kcal mol^?1. A few were identified as the aromatic-thiol hydrogen bond with a bonding energy of 2.0–3.6 kcal mol^?1.     

Chaos control in passive walking dynamics of a compass-gait model

The compass-gait walker is a two-degree-of-freedom biped that can walk passively and steadily down an incline without any actuation. The mathematical model of the walking dynamics is represented by an impulsive hybrid nonlinear model. It is capable of displaying cyclic motions and chaos. In this paper, we propose a new approach to controlling chaos cropped up from the passive dynamic walking of the compass-gait model. The proposed technique is to linearize the nonlinear model around a desired passive hybrid limit cycle. Then, we show that the nonlinear model is transformed to an impulsive hybrid linear model with a controlled jump. Basing on the linearized model, we derive an analytical expression of a constrained controlled Poincaré map. We present a method for the numerical simulation of this constrained map where bifurcation diagrams are plotted. Relying on these diagrams, we show that the linear model is fairly close to the nonlinear one. Using the linearized controlled Poincaré map, we design a state feedback controller in order to stabilize the fixed point of the Poincaré map. We show that this controller is very efficient for the control of chaos for the original nonlinear model.     

Polarization of high spin nuclear levels via tilted multifoil interaction

It has been demonstrated that with suitably spaced carbon foils, tilted with respect to the particle momentum, a large polarization can be generated in high spin nuclei by the tilted foil atomic polarization. Two experiments have been carried out with such polarized high spin isomers: a measurement of the sign of the quadrupole moment of the 10⁺ isomer in⁵⁴Fe, and a new attempt of higher sensitivity at detecting a possible positive parity admixture to the 17/2^– isomer in⁹³Tc.On leave from the Hahn-Meitner Institut, Berlin, W. Germany.On leave from Physics Department, Brooklyn College of the City of New York, Brooklyn, New York.     

The magnetic moment of the 4+, 3.55 MeV level of 18O

The magnetic moment of the 4⁺, 3.55 MeV level of ¹⁸O has been determined to be |g| = 0.62 ± 0.10 in a perturbed angular correlation measurement on nuclei recoiling into gas and vacuum. Analysis of the recoil-into-gas data using the Abragam-Pound model agrees with analysis of the recoil-into-vacuum data using a model for the electronic ensemble described in a previous communication. The value of the g-factor shows the 4⁺ wave function to consist mainly of the$\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}{}^2$ configuration.